CN109999822A - A kind of preparation of the cobaltosic oxide catalyst of carbon nanotube loaded molybdenum doping - Google Patents
A kind of preparation of the cobaltosic oxide catalyst of carbon nanotube loaded molybdenum doping Download PDFInfo
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- CN109999822A CN109999822A CN201910262082.XA CN201910262082A CN109999822A CN 109999822 A CN109999822 A CN 109999822A CN 201910262082 A CN201910262082 A CN 201910262082A CN 109999822 A CN109999822 A CN 109999822A
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- carbon nanotube
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- cobaltosic oxide
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- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 119
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 51
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 41
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 36
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 34
- 239000011733 molybdenum Substances 0.000 title claims abstract description 33
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 15
- 239000010941 cobalt Substances 0.000 claims abstract description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052786 argon Inorganic materials 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 239000003708 ampul Substances 0.000 claims abstract description 3
- 229910052573 porcelain Inorganic materials 0.000 claims abstract description 3
- 239000010453 quartz Substances 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 54
- 238000002604 ultrasonography Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 claims description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 24
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 abstract description 21
- 239000002131 composite material Substances 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 239000002245 particle Substances 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 238000001338 self-assembly Methods 0.000 abstract description 2
- 229910017313 Mo—Co Inorganic materials 0.000 description 36
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000000634 powder X-ray diffraction Methods 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 150000008614 2-methylimidazoles Chemical class 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 4
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002500 ions Chemical group 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- RSRMMPRPLWDSTB-UHFFFAOYSA-N [P].[Na].[Mo] Chemical compound [P].[Na].[Mo] RSRMMPRPLWDSTB-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229940101209 mercuric oxide Drugs 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(II) oxide Inorganic materials [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
-
- B01J35/33—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The present invention relates to a kind of preparations of the cobaltosic oxide catalyst of carbon nanotube loaded molybdenum doping.The preparation method is: using carbon nanotube as conductive substrates, using metal salt containing cobalt as cobalt source, using molybdate as molybdenum source, three is by being self-assembly of the presoma of similar sugarcoated haws shape；Then, quantitative presoma is put in porcelain boat and be encapsulated in quartz ampoule, be passed through high-purity argon gas, first heated up and cool down again, argon gas is changed to air later, is finally naturally cooling to room temperature, be pyrolyzed and aoxidize, obtain target product Mo-Co3O4/CNTs.The preparation method of composite material provided by the invention has many advantages, such as that raw material is easy to get, synthesizes that simple, cost is relatively low, is easy to large scale preparation.The material has particle size smaller, and good conductivity, molybdenum doping are uniform and doping is adjustable；The material is better than commercial iridium dioxide as the catalytic activity of the efficient oxygen-separating catalyst under alkaline condition, and with good stability.
Description
Technical field
The invention belongs to catalyst preparation and application fields, and in particular to a kind of carbon nanotube for electro-catalysis water oxygen
Load the preparation of the cobaltosic oxide catalyst of molybdenum doping.
Background technique
Hydrogen is ecological zero friendly carbon emission due to highest mass energy density, and being considered as comparing has
The energy carrier of prospect.Currently, industry produce hydrogen main method be steam reformation, but should during discharged such as CO, CO2With
And the by-products such as oxynitrides, its environmental-friendly original intention is counteracted significantly.In recent years, cleaner electrochemical catalysis water
It decomposes production hydrogen and has obtained the extensive concern of people.It is well known that electro-catalysis water-splitting is made of two half-reactions: the analysis on cathode
Oxygen evolution reaction in hydrogen reaction and anode.Oxygen evolution reaction on anode is due to being related to polyelectron reaction step, it usually needs compared with
High current potential urges.Currently, some noble metals and its oxide, such as IrC, IrO2And RuO2Etc. being considered as oxygen evolution reaction
The higher catalyst of catalytic activity.But the disadvantages of limited, expensive, durability is poor due to reserves, seriously limit it
Large-scale commercial application.
Cobaltosic oxide draws as a kind of cheap and having the active transition-metal catalyst of oxygen evolution reaction
Play the extensive concern of people.But the electric conductivity of cobaltosic oxide is poor, can reduce its catalytic activity to a certain extent, and
By its with conductive substrates it is compound be improve electric conductivity a kind of simple effective method.Conductive substrates promotion is added in addition to that can pass through
The electric conductivity of material improves outside catalytic activity, can also by seeking to improve the method for the intrinsic catalytic performance of material itself, two
Person's collective effect, to increase substantially catalytic activity.Doping metals atom or ion into the lattice of cobaltosic oxide material
It is to improve the good method of its latent active, this is because the doping of metallic atom or ion can not only adjust the electronics of cobalt atom
Structure, while the active site of material can be increased, to improve catalytic activity.Up to the present, Mn, Fe, Zn and Cu etc. are adulterated
The cobaltosic oxide of transition metal element has been reported.Recently, the non-3d transition metal ions W of high-valence state is had been reported that6+It can lead to
Overregulating electronic structure makes the adsorption energy of 3d transition-metal catalyst tend to optimum value, living come the catalysis for improving catalyst with this
Property.But the catalyst of the cobaltosic oxide of the metal ion mixing of the high-valence state of non-3d is rarely reported.
Class zeolite imidazole skeleton material (ZIFs) obtains in terms of synthesizing porous nano material extensively as a kind of presoma
Using, this is because capableing of the pore structure of reserved materials itself during its high temperature pyrolysis, and there is bigger specific surface area,
The more metal active sites of exposure.Report at present be mostly with material derived from ZIFs it is simple compound with conductive substrates or
The material of simple Heteroatom doping is usually just thought of to single aspect.And using simple and fast method use ZIFs material as
The report for the composite catalyst that precursor synthesis has both conductive substrates and doping effect simultaneously is less.Therefore, preparation method is developed
It is simple and efficient and there is being of great significance based on ZIFs metal oxide nano composite catalyst for good catalytic activity.
Summary of the invention
The object of the present invention is to provide a kind of cobaltosic oxide (Mo-Co of carbon nanotube loaded molybdenum doping3O4/ CNTs)
Preparation method, which can be used as the catalyst of efficient electro-catalysis oxygen evolution reaction, and catalytic effect is good.
Mo-Co of the present invention3O4/ CNTs composite material is first using carbon nanotube as conductive substrates, using metal salt containing cobalt as cobalt
Source, using molybdate as molybdenum source, three is by being self-assembly of presoma POM@ZIF-67/CNTs；Then, under given conditions
It is oxidized, obtains target product Mo-Co3O4/CNTs.It is specific the preparation method is as follows:
1, the preparation of presoma POM@ZIF-67/CNTs
Polyvinylpyrrolidone is dissolved in deionized water first, addition carbon nanotube ultrasonic disperse is uniform, and cobalt source, molybdenum is then added
Source and methanol, ultrasound make it dissolve for about 1 ~ 2 hour.Above-mentioned solution is poured into the methanol solution comprising 2-methylimidazole, stirring 2 ~ 4
Obtained atropurpureus turbid is centrifuged after hour and is washed 3 ~ 6 times with methanol, obtains presoma POM ZIF-67/ after dry
CNTs。
The mass ratio of carbon nanotube and polyvinylpyrrolidone is 1:2 ~ 8 in above-mentioned steps.
Cobalt source described in above-mentioned steps is one of cabaltous nitrate hexahydrate, cobalt acetate and cobalt chloride.
Molybdenum source described in above-mentioned steps is one of phosphomolybdic acid, ammonium molybdate and sodium molybdate.
Cobalt source described in above-mentioned steps and 2-methylimidazole molar ratio are 1:6 ~ 20.
Molybdenum source usage amount is in above-mentioned steps with Mo6+Molal quantity is calculated as 0.01 ~ 0.5 times of cobalt source.
2、 Mo-Co3O4The preparation of/CNTs catalyst
Quantitative POM@ZIF-67/CNTs presoma is put in porcelain boat and is encapsulated in quartz ampoule, leads to high-purity argon gas 0.5 ~ 1 hour to protect
Card material be in argon atmosphere, is warming up to 600 ~ 800 DEG C of holdings 5 ~ 20 minutes with the heating rate of 2 ~ 5 DEG C/min, then with 1.5 ~ 3
Hour is cooled to 200 ~ 500 DEG C and is kept for 1.5 ~ 3 hours, and argon gas is changed to air at this time, is finally naturally cooling to room temperature.It obtains
Black powder is target product Mo-Co3O4/CNTs。
The dosage of POM@ZIF-67/CNTs presoma is 50 ~ 500 mg in above-mentioned steps.
After measured, target product Mo-Co in above-mentioned steps3O4The length of carbon nanotube is 0.5 ~ 2 μm in/CNTs, four oxygen
Change three cobalt granules having a size of 5 ~ 15 nm；Target product Mo-Co in above-mentioned steps3O4Molybdenum doping amount contains in/CNTs for atomic percent
The 2 ~ 8% of amount；Target product Mo-Co in above-mentioned steps3O4The specific surface area of/CNTs is 100 ~ 150 m2 g‒1, total pore volume size
For 0.3 ~ 0.5 cm3 g‒1。
The cobaltosic oxide composite material Mo-Co of carbon nanotube loaded molybdenum doping provided by the invention3O4/ CNTs is as alkali
The catalyst of electro-catalysis water oxidation reaction has the advantage that in property medium
1) the material preparation method raw material is easy to get, synthesizes simply and cost is relatively low, it is easy to accomplish large scale preparation；
2) material has particle size smaller, and good conductivity, molybdenum doping are uniform and doping is adjustable；
3) catalytic activity of the material in electro-catalysis water oxidation reaction is better than commercial iridium dioxide, and has good stabilization
Property.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of presoma POM@ZIF-67/CNTs prepared by the embodiment of the present invention 1.
Fig. 2 is the transmission electron microscope picture of presoma POM@ZIF-67/CNTs prepared by the embodiment of the present invention 1.
Fig. 3 is the X-ray powder diffraction pattern of presoma POM@ZIF-67/CNTs prepared by the embodiment of the present invention 1.
Fig. 4 is Mo-Co prepared by the embodiment of the present invention 13O4The scanning electron microscope (SEM) photograph of/CNTs.
Fig. 5 is Mo-Co prepared by the embodiment of the present invention 13O4The transmission electron microscope picture of/CNTs.
Fig. 6 is Mo-Co prepared by the embodiment of the present invention 13O4The X-ray powder diffraction pattern of/CNTs.
Fig. 7 is Mo-Co prepared by the embodiment of the present invention 13O4The x-ray photoelectron spectroscopy of/CNTs is composed entirely.
Fig. 8 is Mo-Co prepared by the embodiment of the present invention 13O4The high-resolution Co 2p x-ray photoelectron spectroscopy of/CNTs.
Fig. 9 is Mo-Co prepared by the embodiment of the present invention 13O4The high-resolution Mo 3d x-ray photoelectron spectroscopy of/CNTs.
Figure 10 is Mo-Co prepared by the embodiment of the present invention 13O4The N at 77 K of/CNTs2Adsorption curve.
Figure 11 is Mo-Co prepared by the embodiment of the present invention 13O4The pore size distribution curve of/CNTs.
Figure 12 is Mo-Co prepared by the embodiment of the present invention 13O4/ CNTs and business iridium dioxide are 1600 in electrode revolving speed
Linear Circulation volt-ampere curve comparison diagram when rpm.
Figure 13 is Mo-Co prepared by the embodiment of the present invention 13O4/ CNTs and business iridium dioxide are in constant current density 10
mA cm-2When stability volt-time curve comparison diagram.
Specific embodiment
In order to be further understood to method of the invention, illustrated by way of example now in conjunction with attached drawing.Under
Case study on implementation is stated only to specific preparation method of the invention, and is not limited the scope of the invention.
In Fig. 1, the scanning electron microscope (SEM) photograph of presoma POM@ZIF-67/CNTs prepared by the embodiment of the present invention 1 is shown in figure
POM@ZIF-67 is compounded to form the composite construction of similar sugarcoated haws shape with carbon nanotube, and POM@ZIF-67 particle is uniformly applied in
In carbon nanotube, and size is more uniform.
In Fig. 2, the transmission electron microscope picture of presoma POM@ZIF-67/CNTs prepared by the embodiment of the present invention 1 is shown in figure
POM@ZIF-67 particle is uniformly applied in a carbon nanotube, and the air bubble-shaped hole inside POM@ZIF-67 is high-visible.
In Fig. 3, the X-ray powder diffraction pattern of presoma POM@ZIF-67/CNTs prepared by the embodiment of the present invention 1, figure
The characteristic peak of middle display carbon nanotube and POM@ZIF-67, shows the successful preparation of the presoma.
In Fig. 4, the Mo-Co of the preparation of the embodiment of the present invention 13O4The scanning electron microscope (SEM) photograph of/CNTs is shown in resulting materials in figure
The cobaltosic oxide particle of molybdenum doping is evenly distributed on carbon nano tube surface, and size is in 10 rans.
In Fig. 5, the Mo-Co of the preparation of the embodiment of the present invention 13O4The transmission electron microscope picture of/CNTs shows that resulting materials are in figure
Molybdenum doping cobaltosic oxide particle wraps up carbon nano tube structure, and particle size is consistent with scanning electron microscopic observation result.
In Fig. 6, the Mo-Co of the preparation of the embodiment of the present invention 13O4The X-ray powder diffraction pattern of/CNTs, can from figure
There is an apparent bulge for 26 ° or so out, correspond to (002) crystal face of carbon in carbon nanotube, other all characteristic peaks are all with four
The peak of Co 3 O corresponds completely, shows Mo-Co3O4The successful preparation of/CNTs composite material.
In Fig. 7, the Mo-Co of the preparation of the embodiment of the present invention 13O4The x-ray photoelectron spectroscopy of/CNTs is composed entirely, as the result is shown material
Only contain tetra- kinds of elements of C, O, Co and Mo in material.The peak of 220 eV or so is the peak where Mo element, it was demonstrated that resulting materials are molybdenum
The cobaltosic oxide of doping.
In Fig. 8, the Mo-Co of the preparation of the embodiment of the present invention 13O4The high-resolution Co 2p x-ray photoelectron spectroscopy of/CNTs, should
Spectrum can further fit 6 peaks, including the corresponding trivalent cobalt of 779.8/794.7 eV and 781.0/796.3 eV it is corresponding
Divalent cobalt further proves that resulting material is cobaltosic oxide.
In Fig. 9, the Mo-Co of the preparation of the embodiment of the present invention 13O4The high-resolution Mo 3d x-ray photoelectron spectroscopy of/CNTs, should
Spectrum can fit 2 peaks, including 235.0 eV and 231.9 eV, respectively correspond Mo6+3d1/2And 3d3/2, explanation
Molybdenum element mainly with the presence of positive hexavalent form, further proves Mo-Co in the catalyst3O4The successful system of/CNTs composite material
It is standby.
In Figure 10, the Mo-Co of the preparation of the embodiment of the present invention 13O4The N at 77 K of/CNTs2Adsorption curve, therefrom can be with
Find out that micro- mesoporous composite adsorpting type is presented in prepared composite material, maximal absorptive capacity is 102 m2 g-1。
In Figure 11, the Mo-Co of the preparation of the embodiment of the present invention 13O4The pore size distribution curve of/CNTs, as can be seen from the figure institute
The Mo-Co of preparation3O4Micro- mesoporous composite pore structure is presented in/CNTs composite material.
In Figure 12, the Mo-Co of the preparation of the embodiment of the present invention 13O4/ CNTs and business iridium dioxide are 1600 in electrode revolving speed
Linear Circulation volt-ampere curve comparison diagram when rpm, as can be seen from Figure prepared composite material no matter in take-off potential or
It is 10 mA cm in current density-2When two key indexes of overpotential on better than commercialization iridium dioxide catalyst.
In Figure 13, the Mo-Co of the preparation of the embodiment of the present invention 13O4/ CNTs and business iridium dioxide are in constant current density 10
mA cm-2When performance volt-time curve comparison diagram steady in a long-term, as can be seen from the figure prepared composite material is being tested
After 30 hours, voltage only increases 6 mV；And iridium dioxide test 24 hours after, voltage has increased to original twice,
Performance degradation is violent, shows Mo-Co3O4The long-time stability of/CNTs composite material are better than commercialization iridium dioxide.
Embodiment 1
1, the preparation of presoma POM@ZIF-67/CNTs.
300 mg polyvinylpyrrolidones are dissolved at room temperature in 10 mL deionized waters, and 50 mg carbon nanotube ultrasounds are added
It is uniformly dispersed, 0.722 g cabaltous nitrate hexahydrate, 15 mg phosphomolybdic acids and 25 mL methanol is then added, ultrasound keeps its molten in 1 hour
Solution.Then obtained mixed solution is poured into the 25 mL methanol solutions containing 1.629 g 2-methylimidazoles, stirring 2.5
Hour, be centrifuged and wash 3 ~ 6 times with methanol after reaction, at 80 DEG C of vacuum dry 12 hours to get to similar to sugarcoated haws
The presoma of structure is labeled as POM@ZIF-67/CNTs.
2、Mo-Co3O4The preparation of/CNTs catalyst.
The presoma POM@ZIF-67/CNTs(100 mg of similar sugarcoated haws structure) is placed in tube furnace, argon atmosphere
Under with 3 DEG C of heating rates per minute by temperature rise to 700 DEG C and keep the temperature 10 minutes, be then passed through when it is cooled to 400 DEG C
Oxygenous atmosphere is simultaneously down to room temperature after heat preservation 2 hours naturally, and the cobaltosic oxide that carbon nanotube loaded molybdenum doping can be obtained is multiple
Condensation material is labeled as Mo-Co3O4/CNTs。
The scanning electron microscope (SEM) photograph of presoma POM@ZIF-67/CNTs manufactured in the present embodiment is as shown in Fig. 1；
The transmission electron microscope picture of presoma POM@ZIF-67/CNTs manufactured in the present embodiment is as shown in Fig. 2；
The X-ray powder diffraction pattern of presoma POM@ZIF-67/CNTs manufactured in the present embodiment is as shown in Fig. 3；
The standby Mo-Co of the embodiment of the present invention3O4The scanning electron microscope (SEM) photograph of/CNTs is as shown in Fig. 4；
Mo-Co manufactured in the present embodiment3O4The transmission electron microscope picture of/CNTs is as shown in Fig. 5；
Mo-Co manufactured in the present embodiment3O4The X-ray powder diffraction pattern of/CNTs is as shown in Fig. 6；
Mo-Co manufactured in the present embodiment3O4The x-ray photoelectron spectroscopy of/CNTs is composed as shown in Fig. 7 entirely；
Mo-Co manufactured in the present embodiment3O4The high-resolution Co 2p x-ray photoelectron spectroscopy of/CNTs is as shown in Fig. 8；
Mo-Co manufactured in the present embodiment3O4The high-resolution Mo 3d x-ray photoelectron spectroscopy of/CNTs is as shown in Fig. 9；
Mo-Co manufactured in the present embodiment3O4The N at 77 K of/CNTs2Adsorption curve is as shown in Fig. 10；
Mo-Co manufactured in the present embodiment3O4The pore size distribution curve of/CNTs is as shown in Fig. 11.
3、Mo-Co3O4/ CNTs catalyst catalytic performance test in electro-catalysis water oxidation reaction.
Preparation work electrode: by 2.5 mg Mo-Co3O4/ CNTs catalyst is scattered in 600 μ L ethyl alcohol, 375 μ L deionizations
Water and 25 μ L naphthols (5 wt%) mixed solutions, ultrasonic disperse 1 hour, take the 20 above-mentioned dispersant liquid drops of μ L in the straight of dried and clean
Diameter is to dry at room temperature in the ripple carbon electrode of 5 mm.
The preparation of contrast sample: with the preparation method of above-mentioned working electrode, commercialization iridium dioxide catalyst sample is made.
Electro-chemical test mainly includes cyclic voltammetry curve, linear sweep voltammetry curve.Entire test process is in electrochemistry
Carry out on work station, test system is three-electrode system: drop has the ripple carbon electrode of catalyst as working electrode, and platinum filament is as auxiliary
Electrode is helped, for mercury-mercuric oxide electrode as reference electrode, electrolyte is 1 M KOH aqueous solution.Test result is as shown in Fig. 12.
It is 10 mA cm that catalyst long-time stability, which are in constant current density,-2Under the conditions of, the change of test voltage at any time
Change curve.Test result is as shown in Fig. 13.
Embodiment 2
1, the preparation of presoma POM@ZIF-67/CNTs.
200 mg polyvinylpyrrolidones are dissolved at room temperature in 10 mL deionized waters, and 50 mg carbon nanotube ultrasounds are added
It is uniformly dispersed, 0.3 g cabaltous nitrate hexahydrate, 20 mg ammonium molybdates and 25 mL methanol is then added, ultrasound keeps its molten in about 2 hours
Solution.Then obtained mixed solution is poured into the 25 mL methanol solutions containing 1.5 g 2-methylimidazoles, is stirred 3 hours,
It is centrifuged after reacting metal and is washed 3 ~ 6 times with methanol, dry 12 hours at 80 DEG C of vacuum to get to similar to sugarcoated haws knot
The presoma of structure is labeled as POM@ZIF-67/CNTs.
2、Mo-Co3O4The preparation of/CNTs catalyst.
The presoma POM@ZIF-67/CNTs(200 mg of similar sugarcoated haws structure) is placed in tube furnace, argon atmosphere
Under with 5 DEG C of heating rates per minute by temperature rise to 700 DEG C and keep the temperature 30 minutes, be then passed through when it is cooled to 400 DEG C
Oxygenous atmosphere is simultaneously down to room temperature after heat preservation 3 hours naturally, and the cobaltosic oxide that carbon nanotube loaded molybdenum doping can be obtained is multiple
Condensation material is labeled as Mo-Co3O4/CNTs。
Embodiment 3
1, the preparation of presoma POM@ZIF-67/CNTs.
300 mg polyvinylpyrrolidones are dissolved at room temperature in 15 mL deionized waters, and 60 mg carbon nanotube ultrasounds are added
It is uniformly dispersed, 0.35 g cobalt acetate, 10 mg phosphorus molybdenum sodium and 25 mL methanol is then added, ultrasound makes it dissolve for about 1.5 hours.
Then obtained mixed solution is poured into the 25 mL methanol solutions containing 1.64 g 2-methylimidazoles, stirring 3 hours, instead
It is centrifuged after answering metal and is washed 3 ~ 6 times with methanol, dry 12 hours at 80 DEG C of vacuum to get to similar to sugarcoated haws structure
Presoma, be labeled as POM@ZIF-67/CNTs.
2、Mo-Co3O4The preparation of/CNTs catalyst.
The presoma POM@ZIF-67/CNTs(150 mg of similar sugarcoated haws structure) is placed in tube furnace, argon atmosphere
Under with 2 DEG C of heating rates per minute by temperature rise to 700 DEG C and keep the temperature 20 minutes, be then passed through when it is cooled to 400 DEG C
Oxygenous atmosphere is simultaneously down to room temperature after heat preservation 1.5 hours naturally, and the cobaltosic oxide of carbon nanotube loaded molybdenum doping can be obtained
Composite material is labeled as Mo-Co3O4/CNTs。
Example 4
1, the preparation of presoma POM@ZIF-67/CNTs.
150 mg polyvinylpyrrolidones are dissolved at room temperature in 10 mL deionized waters, and 30 mg carbon nanotube ultrasounds are added
It is uniformly dispersed, 0.722 g cabaltous nitrate hexahydrate, 15 mg phosphomolybdic acids and 25 mL methanol is then added, ultrasound makes it in about 1 hour
Dissolution.Then obtained mixed solution is poured into the 25 mL methanol solutions containing 3.258 g 2-methylimidazoles, is stirred
2.5 hours, be centrifuged after reacting metal and wash 3 ~ 6 times with methanol, at 80 DEG C of vacuum dry 12 hours it is similar to get arriving
The presoma of sugarcoated haws structure is labeled as POM@ZIF-67/CNTs.
2、Mo-Co3O4The preparation of/CNTs catalyst.
The presoma POM@ZIF-67/CNTs(100 mg of similar sugarcoated haws structure) is placed in tube furnace, argon atmosphere
Under with 3 DEG C of heating rates per minute by temperature rise to 700 DEG C and keep the temperature 20 minutes, be then passed through when it is cooled to 400 DEG C
Oxygenous atmosphere is simultaneously down to room temperature after heat preservation 2 hours naturally, and the cobaltosic oxide that carbon nanotube loaded molybdenum doping can be obtained is multiple
Condensation material is labeled as Mo-Co3O4/CNTs。
The foregoing is merely representative embodiment of the invention, the interior modification done of all claims according to the present invention
With change, covering scope of the invention all should belong to.
Claims (9)
1. a kind of preparation of the cobaltosic oxide catalyst of carbon nanotube loaded molybdenum doping, it is characterized in that:
1) preparation of presoma POM@ZIF-67/CNTs
Polyvinylpyrrolidone is dissolved in deionized water first, addition carbon nanotube ultrasonic disperse is uniform, and cobalt source, molybdenum is then added
Source and methanol, ultrasound make it dissolve for about 1 ~ 2 hour；Above-mentioned solution is poured into the methanol solution comprising 2-methylimidazole, stirring 2 ~ 4
Obtained atropurpureus turbid is centrifuged after hour and is washed 3 ~ 6 times with methanol, obtains presoma POM ZIF-67/ after dry
CNTs；
2) catalyst Mo-Co3O4The preparation of/CNTs
Quantitative POM@ZIF-67/CNTs presoma is put in porcelain boat and is encapsulated in quartz ampoule, high-purity argon gas is passed through, first heats up and drop again
Argon gas is changed to air later, is finally naturally cooling to room temperature by temperature, obtains target product Mo-Co3O4/CNTs。
2. a kind of preparation of the cobaltosic oxide catalyst of carbon nanotube loaded molybdenum doping according to claim 1, special
Sign is that the mass ratio of the carbon nanotube and polyvinylpyrrolidone is 1:2 ~ 8.
3. a kind of preparation of the cobaltosic oxide catalyst of carbon nanotube loaded molybdenum doping according to claim 1, special
Sign is that the cobalt source is one of cabaltous nitrate hexahydrate, cobalt acetate and cobalt chloride.
4. a kind of preparation of the cobaltosic oxide catalyst of carbon nanotube loaded molybdenum doping according to claim 1, special
Sign is that the molybdenum source is one of phosphomolybdic acid, ammonium molybdate and sodium molybdate.
5. a kind of preparation of the cobaltosic oxide catalyst of carbon nanotube loaded molybdenum doping according to claim 1, special
Sign is that the cobalt source and 2-methylimidazole molar ratio are 1:6 ~ 20.
6. a kind of preparation of the cobaltosic oxide catalyst of carbon nanotube loaded molybdenum doping according to claim 1, special
Sign is the molybdenum source usage amount with Mo6+Molal quantity is calculated as 0.01 ~ 0.5 times of cobalt source.
7. a kind of preparation of the cobaltosic oxide catalyst of carbon nanotube loaded molybdenum doping according to claim 1, special
Sign is passed through high-purity argon gas described in being, being passed through the time is 0.5 ~ 1 hour.
8. a kind of preparation of the cobaltosic oxide catalyst of carbon nanotube loaded molybdenum doping according to claim 1, special
Sign is that the first heating cools down again, and warming temperature is 600 ~ 800 DEG C, and heating rate is 2 ~ 5 DEG C/min, keeps after heating
5 ~ 20 minutes.
9. a kind of preparation of the cobaltosic oxide catalyst of carbon nanotube loaded molybdenum doping according to claim 1, special
Sign is that described cooling down again refers to and was cooled to 200 ~ 500 DEG C with 1.5 ~ 3 hours, is kept for 1.5 ~ 3 hours.
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